The deposition of n-octylphosphonic acid on aluminum oxide was studied. The substrate was pretreated in order to achieve a root-mean-square roughness of <1 nm, a hydroxyl fraction of 30%, and a thickness of approximately 170 nm. It was proven using X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) that, rather than a monolayer, an organic multilayer was formed. The growth mechanism was identified as a Stranski-Krastanov one. It was also shown that the use of AFM, probing the surface topography, is essential for a reliable quantification and interpretation of data obtained with XPS.